Low foaming hard surface cleaners

ABSTRACT

LOW FOAMING HARD SURFACE CLEANER COMPOSITION COMPRISING A FOAMING SURFACTANT, A SEQUESTRANT BUILDER AND, AS A SUDS SUPPRESSOR, THE CONDENSATION PRODUCT OF A STRAIGHT-CHAIN RANDOM SECONDARY ALCOHOL WITH FROM 0 TO ABOUT 3 MOLES OF ETHYLENE OXIDE.

United States Patent 3,679,608 LOW FOAMING HARD SURFACE CLEANERS Harry Julius Aubert, Center Township, Dearborn County, Ind., and Edward Carroll Gemperle, Cincinnati, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio No Drawing. Filed Aug. 2, 1968, Ser. No. 749,597 Int. Cl. Clld 3/075 U.S. Cl. 252-526 5 Claims ABSTRACT OF THE DISCLOSURE low foaming hard surface cleaner composition comprising a foaming surfactant, a sequestrant builder and, as a suds suppressor, the condensation product of a straight-chain random secondary alcohol with from O to about 3 moles of ethylene oxide.

FIELD 'OF THE INVENTION PRIOR ART Secondary alkyl ethoxylates are old having been disclosed in U.S. Pat. 2,355,823. The combination of alkyl ethoxylates and diethanolamides is disclosed in U.S. Pat. 2,831,815 which discloses that the amides improve the sudsing of alkyl ethoxylates having at least 5 ethylene oxide moieties per alkyl ethoxylate molecule. This patent, however, does not disclose that certain specific secondary alkyl ethoxylates will act as suds suppressors when mixed with amides. The combination of certain zwitterionic detergents and alkyl ethoxylates is disclosed in U.S. Pat. 3,351,557. This patent also does not disclose secondary alkyl ethoxylates specifically. 'None of the prior art patents disclose that there is any criticality, with respect to reduced sudsing, in selecting secondary alkyl ethoxylates for use with certain specific sudsing surfactants.

SUMMARY OF THE INVENTION The compositions of this invention are low-foaming hard-surface cleaner compositions consisting essentially of:

(a) From about 1% to about of a primary surfactant selected from the group consisting of:

(1) the condensation product of a straight chain primary alcohol containing from about 8 carbon atoms to about '16 carbon atoms and having an average carbon chain length of from about 10 to about 12 carbon atoms with from about 4 to about 8 moles of ethylene oxide per mole of alcohol,

(2) an amide having the formula Rd-N(R )2 wherein R is a straight chain alkyl group containing from about 7 to about 15 carbon atoms and having an average carbon chain length of from about 9 to about 13 carbon atoms and wherein each R is a hydroxyalkyl group containing from 1 to about 3 carbon atoms,

(3) a zwitterionic surfactant having the formula 3,679,608 Patented July 25, 1972 "ice wherein R contains from about 8 to about 16 carbon atoms and has an average of from about 10 to about 13 carbon atoms, each R is selected from the group consisting of alkyl and hydroxy alkyl groups containing from 1 to about 3 carbon atoms, and R is a saturated alkylene or hydroxyalkylene group containing from 2 to about 5 carbon atoms and wherein the hydroxy group in said hydroxyal'kylene group is attached to a carbon atom which is separated from the nitrogen atom by at least one methylene group, (4) a phosphine oxide surfactant having the formula g E F-(RD:

wherein R contains from about 8 to about 16 carbon atoms and has an average of from about 10 to about 12 carbon atoms and wherein each R is selected from the group consisting of alkyl and hydroxy alkyl groups containing from 1 to about 3 carbon atoms, and

(5) Mixtures thereof;

(b) From about 1% to about 3% of a suds suppressor and surfactant which is the condensation product of a straight chain random secondary alcohol having a chain length of from about 11 to about 15 carbon atoms and having an average length of from about 12 to about 15 carbon atoms with from 0 to about 3 moles of ethylene oxide;

(c) From about 10% to about 50% of a sequestrant builder selected from the group consisting of alkali metal and ammonium aminopolycarboxylates, organic polyphosphonates, polymeric carboxylates, pyrophosphates and tripolyphosphates;

(d) From 0% to about 80% of a salt selected from the group consisting of alkali metal and ammonium carbonates, sesquicarbonates, bicarbonates, borax and mixtures thereof;

(e) From 0% to about 12% of a hydrotroping agent selected from the group consisting of alkali metal, ammonium, and triethanolammonium isopropylbenzene sulfonates, xylene sulfonates, toluene sulfonates, and benzene sulfonates, and mixtures thereof; and

(f) The balance water, the ratio of (a) to (b) being from about 4:1 to about 0.7:1 and the ratio of the sum of (a) and (b) to (c) being from about 1:2 to about 1:10.

The amount of the primary surfactant in the compositions of this invention is determined by the cleaning requirements and the type of product desired. There is usually from about 1% to about 10% of this component in the composition. When the product is in the form of a liquid, however, it is preferred that the primary surfactant range from about 2% to about 5%, more preferably from about 2% to about 3%, of the composition.

Specific examples of suitable primary surfactants are given hereinafter in the examples.

There is a definite relationship between the amount of primary surfactant and the suds suppressor. There is from about 1% to about 3%, preferably from about 1% to about 2% of the suds suppressor in the composition and the ratio of primary surfactant to suds suppressor ranges from about 4:1 to about 0.7:1, preferably from about 2:1 to about 1:1, and most preferably from about 1.5 :1 to about 1:1. The preferred ratio is 1.5 1. The suds suppressor keeps down the level of suds when the prodnet is being used to clean hard surfaces in a diluted form and more importantly it suppresses sudsing when the product is being diluted in the housewifes bucket under conditions which involve higher concentrations of surfactant and greater agitation. The housewife wants a minimum amount of suds in a hard surface cleaner, especially where the housewife does not rinse the surface after the washing step. The suds suppressor of this invention lowers the level of suds for the specific primary surfactants of this invention, but not for conventional anionic synthetic surfactants such as alkyl benzene sulfonates. Furthermore, if the corresponding primary alkyl ethoxylate is used instead of the random secondary alkyl ethoxylate, the reduction in sudsing, especially during dilution in the bucket, is much less pronounced. This is totally unexpected. These suds suppressors do not harm the cleaning effectiveness of the composition and even contribute to the cleaning effect. The preferred suds suppressor is the condensation product of a random secondary straight chain alcohol having from about 11 to about carbon atoms and an average of about 13 carbon atoms with about 3 moles of ethylene oxide per mole of alcohol.

The compositions also contain a sequestering builder. Suitable builders include the alkali metal (e.g., sodium and potassium) and ammonium (including substituted ammonium, e.g., triethanolammonium) aminopolycarboxylates, organic polyphosphonates, polymeric carboxylates, pyrophosphates, and tripolyphosphates. Suitable aminopolycarboxylates are those described in US. Pats. Nos. 3,329,617 and 3,336,233. Suitable polyphosphonates are those described in US. Pats. Nos.: 3,329,617; 3,336,- 233; 3,332,880 and 3,213,030; copending US. applications: Roy, Ser. No. 266,055 filed Mar. 18, 1963 US. Pat. No. 3,422,021; Roy, Ser. No. 493,925 filed Mar. 18, 1963 US. Pat. No. 3,404,178; Quimby, Ser. No. 489,637 filed Sept. 23, 1965 US. Pat. No. 3,400,148; Quimby, Ser. No. 507,662 filed Nov. 15, 1965 US. Pat. No. 3,400,- 176; Quimby, Ser. No. 517,073 filed Dec. 28, 1965 US. Pat. No. 3,422,137; Quimby and Prentice, Ser. No. 587,- 417 filed Oct. 18, 1966 now abandoned; Quimby, Ser. No. 605,606 filed Dec. 29, 1966 US. Pat. No. 3,497,313; Curry, Ser. No. 717,999 filed Apr. 1, 1968 now abandoned; Nicholson and Campbell, Ser. No. 694,002 filed Dec. 27, 1967 now abandoned; Nicholson and Campbell, Ser. No. 694,003 filed Dec. 27, 1967 now abandoned; Prentice and Quimby, Ser. No. 694,112 filed Dec. 28, 1967 U.S. Pat. No. 3,400,151; and Prentice and Quimby, Ser. No. 694,106 filed Dec. 28, 1967 US. Pat. No. 3,512,- 862. Suitable polymeric carboxylates are disclosed in US.

liquid, it is desirable to have from about 2% to about 12% of a hydrotroping agent to keep the composition homogeneous under varying storage conditions. Mixtures of alkali metal, ammonium and/ or triethanolammonium isopropyl benzene sulfonate and the equivalent salts of either xylene, toluene or benzene sulfonate in ratios of from about 10:1 to about 0.5:1 are preferred since they are more effective than the individual hydrotropes. The isopropyl benzene sulfonate is also effective.

The compositions can also be in the form of stable emulsions. For such emulsions, the hydrotrope should be omitted and an emulsion stabilizer added in amounts from about 0.5% to about 2%, preferably from about 0.8% to about 1.5%. Acrysol ASE-J08, a commercial product, is preferred. The compositions can also contain numerous miscellaneous ingredients such as dyes, pigments, perfumes, ammonia, etc.

The following examples demonstrate the advantages of this invention, but should not be taken as limiting its scope.

EXAMPLE I The compositions listed in the following table were tested for cleaning hard surfaces, the amount of suds produced on the surfaces cleaned, and the amount of suds generated when the compositions were diluted with water in a bucket. All of the compositions cleaned the surfaces well and gave acceptably low suds on the surfaces cleaned. However, the amount of suds generated in the bucket varied remarkably depending on whether a. secondary alcohol ethoxylate or a primary alcohol ethoxylate was used.

The bucket sudsing values given are the average of the inches of suds produced when two tests were run on each composition. In both tests the dilution rate was A cup of product in one gallon of water. The two tests are as follows: In the first the detergent composition is added first, then the water is added from a tap at a standard height and the suds measured. In the second test the Water is added first, then the detergent is added and agitation is provided by repeating five times in a. minute the steps of dipping a sponge into the water and then wringing it out; the suds are then measured.

Composition 1 2 3 4 5 6 7 8 9 The condensation product of a primary straight chain alcohol (Cg-C12) containing an average of about 10 carbon atoms and about 7 moles of ethylene oxide per mole of alcohol 3 Fatty acid diethanolamide containing fatty acyl groups (Cw-On) with an average of about 11 carbon atoms 3 3 Decyldimethylphosphine oxide 3 3 The condensation product of a primary straight chain alcohol (CB-C12) having an average of about 10 carbon atoms and about 4 moles of ethylene oxide per mole of alcohol 3 3 per mole of alcohol 3-[N-coconut; 1 alkyl-N,N-dimethylammonio]-2 hydroxypropane-l-sulfonate.. .2:III:IIIIIIIIIIIIII III: 3 3

The condensation product of a random secondary straight chain alcohol (011'015) containing an average of about 13 carbon atoms and about three moles of ethylene oxide per mole of alcohol Potassium pyrophosphate Sodium carbonate Potassium toluene sulfona Sodium cumene sulionate. Acrysol ASE-108 Bucket sudsing (inches of suds) .I:

Balance 2.9 0.7 1.9 1.25 24 1 Coconut refers to a chain length distribution substantially as follows:

Pat. No. 3,308,067. All of the above patents and applications are incorporated herein by reference.

Preferred sequestering builders are sodium nitrilotriacetate, potassium pyrophosphate, potassium tripolyphosphate, and sodium or potassium ethane-1-hydroxy-l,1- diphosphonate.

Sodium carbonate or other alkaline salts are added to the compositions, in amounts up to about 80% as pH buffers. In liquid compositions there should be from about 1% to about 5% sodium carbonate. Other pH bufiers can be used including sodium sesquicarbonate, borax, etc., but sodium carbonate is preferred for many reasons such as availability and cost.

When the composition is in the form of a homogeneous The compositions containing the secondary alcohol ethoxylates (2, 4, 5, 8, and 10) all gave lower bucket sudsing than the compositions containing the primary alcohol ethoxylates (1, 3, and 7) and the compositions containing no suds suppressor (6 and 9).

The above compositions clearly demonstrate the unobvious advantages, with respect to bucket sudsing, of the secondary alkyl ethoxylates as compared with the primary alkyl ethoxylates.

The following compositions give results which are substantially similar to those obtained with the preceding compositions in that the bucket sudsing is less when the compositions contain the indicated straight-chain random secondary alcohol ethoxylates rather than the corresponding primary alcohol ethoxylates and the bucket sudsing is also less for the compositions containing the straightchain random secondary alcohol ethoxylates than for similar compositions without the secondary alcohol ethoxylates.

EXAMPLE II Solid granular Percent Ethoxylated moles) primary alcohol (C and C P-1:1 mixture) Decyldi (Z-hydroxyethyl)phosphineoxide 2 Dodecyldimethylphosphineoxide 2 Ethoxylated (2 moles) straight-chain random secondary alcoh 13) 4- Sodium tripolyphosphate 4-12---- 26 Sodium sesquicarbonate 30 Borax EXAMPLE III Liquid Percent 3 [N,N dimethyl N-decylammonio]-propane-lsulfonate Ethoxylated (8 moles) primary alcohol (C 1 Ethoxylated (3 moles) straight-chain random secondary alcohol (C 2 Ammonium ethylenediaminetetraacetate 0.5

Triethanolam-monium poly(itaconate-acrylate) (4:1 on a molar basis) (specific viscosity of 1% by weight, in dimethyl formamide at room temperature, .40) (equivalent weight, 65.8) 10 Sodium polyitaconate (specific viscosity of 1% by weight in dimethylformamide at room temperature,

Potassium polymaleate (specific viscosity of 1% by weight in dimethylformamide at room temperature,

.13) (equivalent weight as acid, 58) 10 Potassium ethane-1,1,2-triphosphonate 10 Sodium carbonate 2 Triethanolammonium cumene sulfonate 4 Water Balance EXAMPLE V Liquid Percent 4 [N,N' di(2-hydroxyethyl)-N-dodccylammonio]- Z-hydroxybutane-l-sulfonate 3 4 [N,N' diethyl N undecylammonio] -butane-1- sulfonate 1 Ethoxylated (2.5 moles) straight-chain random secondary alcohol (C 1. Potassium ethane-l-hydroxy-l,l,2-triphosphonate Ammonium ethane-2-hydroXy-1,1,2-triphosphonate Tripotassium ethane-l-hydroxy-1,1-diphosphonate Sodium carbonate Potassium cumene sulfonate Potassium toluene sulfonate Water Balance EXAMPLE Vl Solid Percent 3[N,N'-dimethylol-N-alkyl(l:1:1 C11, C and (C ammonio]-2-hydroxypropane-l-sulfonate Ethoxylated (7 moles) primary alcohol (1: 1:1 C C and C13) Ethoxylated (3 moles) straight-chain random secondary alcohol (C -C C average) 3 Sodium tripolyphosphate 15 Sodium nitrilotriacetate 15 Trisodiu-m ethane-l-hydroxy-1,1-diphosphonate 15 Sodium sesquicarbonate 30 Borax 16 EXAMPLE VII Liquid Percent 3 [N,N' dimethyl N-coconut alkylammonio]-2- hydroxypropane-l-sulfonate 2 Ethoxylated (7 moles) primary coconut alcohol 2 Straight-chain random secondary alcohol (C -C C average) 1 Sodium nitrilotriacetate 5 Potassium tripolyphosp'hate 10 Potassium cumene sulfonate 4 Potassium toluene sulfonate 4 Sodium carbonate 4 Water Balance *Coconut refers to a. chain length distribution substantially as follows: =2%-C1o, G6%-C12, 23%-C14, and 9%-C1a.

EXAMPLE VIII Liquid Percent 3-[N,N' dimethyl-N-decylammonio]-propane-l-sulfonate 2 Ethoxylated (5 moles) n-decyl alcohol 3 Ethoxylated (2 moles) straight-chain random secondary alcohol (C 1 Potassium pyrophosphate 15 Potassium Xylene sulfonate 6 Sodium carbonate 3 Water Balance EXAMPLE IX Solid Percent Fatty acid (C di(isopropanol)amide 3 Fatty acid (C dimethanolamide 3 Fatty acid (C dimethylamide 3 Ethoxylated (1 mole) straight-chain random secondary alcohol (C 3 Sodium methylene-diphosphonate 2 Potassium tripolyphosphate 4 Potassium carbonate 10 Sodium ethylene-1,l-diphosphonate 2 Potassium benzylmethylidene diphosphonate 1 Sodium N-(2 hydroxyethyl)-ethylenediaminetriacetate 2 Sodium N-(Z-hydroxyethyD-nitrilo diacetates 2 Potassium isopropylidene diphosphonate 1 Potassium ethylidene diphosphonate 1 Sodium orthophosphate 4 Potassium ethane-Z-carboxy-l,l-diphosphonate 1 Potassium hydroxymethanediphosphonate 1 Ammonium propane-1,1,3,3-tetraphosphonate 1 Ammonium propane-1,2,2,3-tetraphosphonate 1 Ammonium propane-1,1,2,3-tetraphosphonate 1 Ammonium carbonyldiphosphonate 2 Sodium hexametaphosphate 5 Sodium sesquicarbonate 10 Borax Balance EXAMPLE X Liquid Percent [N-( 3 hydroxypropyl) -N- 2-hydroxypropyl-N-tridecylammonio] -3-hydroxypentanel-sulfonate 1 Decyl (3 hydroxypropyl) (2 hydroxypropyl)phosphine oxide Octyldiethylphosphine oxide 1 Ethoxylated (1.5 moles) straight-chain random secondary alcohol (C l Triethanol ammonium toluene sulfonate 6 Potassium pyrophosphate 12 Water Balance All parts, ratios, and percentages herein are by weight unless otherwise specified.

What is claimed is: 1. A low-foaming hard-surface cleaner composition consisting essentially of:

(a) from about 1% to about of a primary surfactant selected from the group consisting of:

(1) the condensation product of a straight chain primary alcohol containing from about 8 to about 16 carbon atoms and having an average carbon chain length of from about 10 to about 12 carbon atoms with from about 4 to about 8 moles of ethylene oxide per mole of alcohol,

(2) an amide having the formula wherein R is a straight chain alkyl group containing from about 7 to about carbon atoms and having an average carbon chain length of from about 9 to about 13 carbon atoms and wherein each R is a hydroxyalkyl group containing from 1 to about 3 carbon atoms,

(3) a zwitterionic surfactant having the formula wherein R contains from about 8 to about 16 carbon atoms and has an average of from about 10 to about 13 carbon atoms, each R is selected from the group consisting of alkyl and hydroxy alkyl groups containing from 1 to about 3 carbon atoms, and R is selected from the group consisting of a saturated alkylene group and a saturated hydroxyalkylene group containing from 2 to about 5 carbon atoms and wherein the hydroxy group in said hydroxy alkylene group is attached to a carbon atom which is separated from the nitrogen atom by at least one methylene group,

(4) a phosphine oxide surfactant having the formula o T R5P(R):

wherein R contains from about 8 to about 16 carbon atoms and has an average of from about 10 to about 12 carbon atoms and wherein each R is selected from the group consisting of alkyl and hydroxy alkyl groups containing from 1 to about 3 carbon atoms, and

(5) mixtures thereof;

(b) from about 1% to about 3% of a suds suppressor and surfactant which is the condensation product of a mixture of straight-chain random secondary alcohols having a chain length of from about 11 to about 15 carbon atoms, said alcohols having an average chain length of from about 12 to about 15 carbon atoms with about 3 moles of ethylene oxide;

(c) from about 10% to about 50% of a sequestrant detergency builder selected from the group consisting of alkali metal and ammonium aminopolycarboxylates, organic polyphosphonates, polymeric carboxylates, pyrophosphates and tripolyphosphates;

(d) from 0% to about of a salt selected from the group consisting of alkali metal and ammonium carbonates, sesquicarbonates, bicarbonates, borax, and mixtures thereof;

(e) from 0% to about 12% of a hydrotroping agent selected from the group consisting of alkali metal, ammonium, and triethanolammonium isopropylbenzene sulfonates, toluene sulfonates, xylene sulfonates, and benzene sulfonates and mixtures thereof; and

(f) water, the ratio of (a) to (b) being from about 4:1 to about 0.7:1 and the ratio of the sum of (a) and (b) to (c) being from about 1:2 to about 1:10.

2. The composition of. claim 1 wherein the sequestering detergency builder is selected from the group consisting of sodium nitrilotriacetate, potassium pyrophosphate, potassium tripolyphosphate, and sodium or potassium ethane-l-hydroxy-1,1-diphosphonate.

3. The composition of claim 1 in the form of a homogeneous liquid containing (1) from about 2% to about 5% of component (a);

(2) from about 1% to about 2% of component (b);

(3) from about 10% to about 20% of component (c);

(4) from about 1% to about 5% sodium carbonate;

(5) from about 2% to about 12% of component (e);

and

(6) the balance water, and the ratio of component (a) to component (b) is from about 2:1 to about 1:1.

4. The composition of claim 3 wherein the sequestering detergency builder is selected from the group consisting of sodium nitrilotriacetate, potassium pyrophosphate, potassium tripolyphosphate, and sodium or potassium ethane-l-hydroxy-1,1diphosphonate.

5. The composition of claim 3 wherein there is from about 2% to about 3% of component (a) and the ratio of component (a) to component (b) is from about 1.5 :1 to about 1:1.

References Cited UNITED STATES PATENTS 2,355,823 8/ 1944 Schlegel 252-89 X 2,751,358 6/1956 Caviet 252-153 2,831,815 4/1958 Klisch 252-152 2,867,585 1/1959 Vitale 252-89 X 3,008,905 11/1961 Wedell 252-152 X 3,052,635 9/1962 Wixon 252-137 3,454,494 7/1969 Clark et a1. 252-137 X 3,549,539 12/ 1970 Mallows 252-99 3,356,613 12/1967 Gedge 252-137 FOREIGN PATENTS 830,875 3/ 1960 Great Britain 252-89 540,798 5/1957 Canada 252-89 OTHER REFERENCES Technical Bulletin, Rohn & Haas, Acrysol ASE-95, August 1965, p. 1.

McCutcheon: Detergents and Emulsifiers, 1968 Annual, p. 225.

Tergitol S Series, Technical Bulletin, Union Carbide Corp., N.Y., Mar. 2, 1964, #F-41073 A, pp. 1-3.

LEON D. ROSDOL, Primary Examiner A. I. RADY, Assistant Examiner US. Cl. X.R.

STATES PATENT W EER'NFECATE @E CQREUMWN Patent No. 3,679,608 Dated July 25, 1972 Inventor) Harry Julius Aubert and Edward Carroll Gemp'erle It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

f4. i Col. 3, lines 43 and 44, "3,512 ,862" shoulo; reac;

Signed. and sealedthis 23rd day of January 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N 3,679,608 Dated July 25, 1972 Inventor) Harry Julius Aubert and Edward Carroll Gemp'erle It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

F Col. 3, lines 43 and 44, 3,512,862" should read Signed and sealed.this 23rd day of January 1973.

(SEAL) Attest:

EDWARD 1 I.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

